Active agent combinations with insecticidal and acaricidal properties

ABSTRACT

The invention relates to novel active compound combinations having very good insecticidal and acaricidal properties and containing
     (a) cyclic ketoenols having the formula   

     
       
         
         
             
             
         
       
         
         
           
             in which the groups W, X, Y, Z, A, B, D, and G have the meanings given in the disclosure, and 
           
         
         (b) the active compounds (1) to (29) listed in the disclosure.

The present invention relates to novel active compound combinationscomprising known cyclic ketoenoles on the one hand and other knowninsecticidally active compounds on the other hand and which are highlysuitable for controlling animal pests such as insects and undesiredacarids.

It is already known that certain cyclic ketoenoles have herbicidal,insecticidal and acaricidal properties. The activity of these substancesis good; however, at low application rates it is sometimesunsatisfactory.

Unsubstituted bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP-A-355 599 and EP-A-415 211) and substituted monocyclic3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077)are known to have herbicidal, insecticidal or acaridical activity.

Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives(EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063,EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43 275, WO 98/05 638, WO98/06 721, WO 98/25 928, WO 99/16 748, WO 99/24 437, WO 99/43 649, WO99/48 869 and WO 99/55 673).

Furthermore, it is already known that numerous heterocycles, organotincompounds, benzoylureas and pyrethroids have insecticidal and acaricidalproperties (cf. WO 93/22 297, WO 93/10 083, DE-A 2 641 343, EP-A-347488, EP-A-210 487, U.S. Pat. No. 3,264,177 and EP-A-234 045). However,the activity of these substances is not always satisfactory.

It has now been found that compounds of the formula (I)

in which

-   X represents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy    or cyano,-   W, Y and Z independently of one another each represent hydrogen,    halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or cyano,-   A represents hydrogen, in each case optionally halogen-substituted    alkyl, alkoxyalkyl, saturated, optionally substituted cycloalkyl in    which optionally at least one ring atom is replaced by a heteroatom,-   B represents hydrogen or alkyl,-   A and B together with the carbon atom to which they are attached    represent a saturated or unsaturated, unsubstituted or substituted    cycle which optionally contains at least one heteroatom,-   D represents hydrogen or an optionally substituted radical from the    group consisting of alkyl, alkenyl, alkoxyalkyl, saturated    cycloalkyl in which optionally one or more ring members are replaced    by heteroatoms,-   A and D together with the atoms to which they are attached represent    a saturated or unsaturated cycle which is unsubstituted or    substituted in the A, D moiety and optionally contains at least one    heteroatom,-   G represents hydrogen (a) or represents one of the groups

in which

-   -   E represents a metal ion or an ammonium ion,    -   L represents oxygen or sulphur,    -   M represents oxygen or sulphur,    -   R¹ represents in each case optionally halogen-substituted alkyl,        alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or        optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl        which may be interrupted by at least one heteroatom, in each        case optionally substituted phenyl, phenylalkyl, hetaryl,        phenoxyalkyl or hetaryloxyalkyl,    -   R² represents in each case optionally halogen-substituted alkyl,        alkenyl, alkoxyalkyl, polyalkoxyalkyl or represents in each case        optionally substituted cycloalkyl, phenyl or benzyl,    -   R³ represents optionally halogen-substituted alkyl or optionally        substituted phenyl,    -   R⁴ and R⁵ independently of one another each represent in each        case optionally halogen-substituted alkyl, alkoxy, alkylamino,        dialkylamino, alkylthio, alkenylthio, cycloalkylthio or        represent in each case optionally substituted phenyl, benzyl,        phenoxy or phenylthio and    -   R⁶ and R⁷ independently of one another each represent hydrogen,        in each case optionally halogen-substituted alkyl, cycloalkyl,        alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted        phenyl, represent optionally substituted benzyl or together with        the N atom to which they are attached represent an optionally        substituted ring which is optionally interrupted by oxygen or        sulphur        and acaricidally active compounds, preferably        (1) the phenylhydrazine derivative of the formula

known from WO 93/10 083

and/or(2) the macrolide with the common name

abamectin  (III)

known from DE-A-27 17 040

and/or(3) the naphthalinedione derivative of the formula

known from DE-A-26 41 343

and/or(4) the pyrrole derivative of the formula

known from EP-A-347 488

and/or(5) the thiourea derivative of the formula

known from EP-A-210 487

and/or(6) the oxazoline derivative of the formula

known from WO 93/22 297

and/or(7) an organotin derivative of the formula

in which

R represents

-   -   known from The Pesticide Manual, 9th edition, p. 48

or

R represents —OH

-   -   (VIIIb=cyhexatin),    -   known from U.S. Pat. No. 3,264,177        and/or        (8) the pyrazole derivative of the formula

known from EP-A-289 879

and/or(9) the pyrazole derivative of the formula

known from EP-A-234 045

and/or(10) the pyridazinone derivative of the formula

known from EP-A-134 439

and/or(11) the benzoylurea of the formula

known from EP-A-161 019

and/or(12) the pyrethroid of the formula

known from EP-A-049 977

and/or(13) the tetrazine derivative of the formula

known from EP-A-005 912

and/or(14) the organotin derivative of the formula

known from DE-A-2 115 666

and/or(15) the sulphenamide of the formula

known from The Pesticide Manual, 11th edition, 1997, page 1208

(16) and/or the pyrimidyl phenol ethers

R=Cl  (XVII);

-   (4-[(4-chloro-α,α,α-trifluoro-3-tolyl)oxy]-6-[(α,α,α-4-tetrafluoro-3-tolyl)oxy]-pyrimidine)

R=NO₂  (XVIII);

-   4-[(4-chloro-α,α,α-trifluoro-3-tolyl)oxy]-6-[(α,α,α-trifluoro-4-nitro-3-tolyl)oxy]-pyrimidine

R=Br  (XIX);

-   4-[(4-chloro-α,α,α-trifluoro-3-tolyl)oxy]-6-[(α,α,α-trifluoro-4-bromo-3-tolyl)oxy]-pyrimidine

known from WO 94/02 470, EP-A-883 991

and/or

(17) the macrolide of the formula

(spinosad) a mixture preferably comprising

85% of spinosyn A R═H 15% of spinosyn B R═CH₃

known from EP-A-375 316

and/or

(18) ivermectin  (XXI)

known from EP-A-001 689

and/or

(19) milbemectin  (XXII)

known from The Pesticide Manual, 11th edition, 1997, p. 846

and/or

(20) endosulfan  (XXIII)

known from DE-A-1 015 797

and/or

(21) fenazaquin  (XXIV)

known from EP-A-326 329

and/or

(22) pyrimidifen  (XXV)

known from EP-A-196 524

and/or

(23) triarathen  (XXVI)

known from DE-A-2 724 494

and/or

(24) tetradifon  (XXVII)

known from U.S. Pat. No. 2,812,281

and/or

(25) propargit  (XXVIII)

known from U.S. Pat. No. 3,272,854

and/or

(26) hexythiazox  (XXIX)

known from DE-A-3 037 105

and/or

(27) bromopropylate  (XXX)

known from U.S. Pat. No. 3,784,696

and/or

(28) dicofol  (XXXI)

known from U.S. Pat. No. 2,812,280

and/or

(29) chinomethionat  (XXXII)

known from DE-A-1 100 372

have very good insecticidal and acaricidal properties.

Surprisingly, the insecticidal and acaricidal action of the activecompound combinations according to the invention considerably exceedsthe total of the actions of the individual active compounds. A truesynergistic effect which could not have been predicted therefore exists,not just a complementation of action.

The active compound combinations according to the invention comprise, inaddition to at least one active compound of the formula (I), at leastone active compound of compounds 1 to 29.

Preference is given to active compound combinations comprising compoundsof the formula (I) in which the radicals are as defined below:

-   W preferably represents hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,    chlorine, bromine or fluorine,-   X preferably represents C₁-C₄-alkyl, C₁-C₄-alkoxy,    C₁-C₄-halogenoalkyl, fluorine, chlorine or bromine,-   Y and Z independently of one another each preferably represent    hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy or C₁-C₄-halogenoalkyl,-   A preferably represents hydrogen or in each case optionally    halogen-substituted C₁-C₆-alkyl or C₃-C₈-cycloalkyl,-   B preferably represents hydrogen, methyl or ethyl,-   A, B and the carbon atom to which they are attached preferably    represent saturated C₃-C₆-cycloalkyl in which optionally one ring    member is replaced by oxygen or sulphur and which is optionally    mono- or disubstituted by C₁-C₄-alkyl, trifluoromethyl or    C₁-C₄-alkoxy,-   D preferably represents hydrogen, in each case optionally fluorine-    or chlorine-substituted C₁-C₆-alkyl, C₃-C₄-alkenyl or    C₃-C₆-cycloalkyl,-   A and D together preferably represent optionally methyl-substituted    C₃-C₄-alkanediyl in which optionally one methylene group is replaced    by sulphur,-   G preferably represents hydrogen (a) or represents one of the groups

in particular (a), (b), (c) or (g)

in which

E represents a metal ion or an ammonium ion,

L represents oxygen or sulphur and

M represents oxygen or sulphur,

-   R¹ preferably represents in each case optionally halogen-substituted    C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,    C₁-C₄-alkylthio-C₁-C₄-alkyl or optionally fluorine-, chlorine-,    C₁-C₄-alkyl- or C₁-C₂-alkoxy-substituted C₃-C₆-cycloalkyl,

represents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-,C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl- ortrifluoromethoxy-substituted phenyl,

represents in each case optionally chlorine- or methyl-substitutedpyridyl or thienyl,

-   R² preferably represents in each case optionally fluorine- or    chlorine-substituted C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl,    C₁-C₄-alkoxy-C₂-C₄-alkyl,

represents optionally methyl or methoxy-substituted C₅-C₆-cycloalkyl or

represents in each case optionally fluorine-, chlorine-, bromine-,cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl- ortrifluoromethoxy-substituted phenyl or benzyl,

-   R³ preferably represents optionally fluorine-substituted C₁-C₄-alkyl    or represents optionally fluorine-, chlorine-, bromine-,    C₁-C₄-alkyl-, C₁-C₄-alkoxy-, trifluoromethyl-, trifluoromethoxy-,    cyano- or nitro-substituted phenyl,-   R⁴ preferably represents in each case optionally fluorine- or    chlorine-substituted C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,    C₁-C₄-alkylthio or represents in each case optionally fluorine-,    chlorine-, bromine-, nitro-, cyano-, C₁-C₄-alkoxy-,    trifluoromethoxy-, C₁-C₄-alkylthio-, C₁-C₄-halogenoalkylthio-,    C₁-C₄-alkyl- or trifluoromethyl-substituted phenyl, phenoxy or    phenylthio,-   R⁵ preferably represents C₁-C₄-alkoxy or C₁-C₄-thioalkyl,-   R⁶ preferably represents C₁-C₆-alkyl, C₃-C₆-cycloalkyl,    C₁-C₆-alkoxy, C₃-C₆-alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,-   R⁷ preferably represents C₁-C₆-alkyl, C₃-C₆-alkenyl or    C₁-C₄-alkoxy-C₁-C₄-alkyl,-   R⁶ and R⁷ together preferably represent an optionally methyl- or    ethyl-substituted C₃-C₆-alkylene radical in which optionally one    carbon atom is replaced by oxygen or sulphur,-   W particularly preferably represents hydrogen, methyl, ethyl,    chlorine, bromine or methoxy,-   X particularly preferably represents chlorine, bromine, methyl,    ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl,-   Y and Z independently of one another each particularly preferably    represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl,    propyl, i-propyl, trifluoromethyl or methoxy,-   A particularly preferably represents methyl, ethyl, propyl,    i-propyl, butyl, i-butyl, sec-butyl, tert-butyl, cyclopropyl,    cyclopentyl or cyclohexyl,-   B particularly preferably represents hydrogen, methyl or ethyl,-   A, B and the carbon atom to which they are attached particularly    preferably represent saturated C₆-cycloalkyl in which optionally one    ring member is replaced by oxygen and which is optionally    monosubstituted by methyl, ethyl, methoxy, ethoxy, propoxy or    butoxy,-   D particularly preferably represents hydrogen, represents methyl,    ethyl, propyl, i-propyl, butyl, i-butyl, allyl, cyclopropyl,    cyclopentyl or cyclohexyl,-   A and D together particularly preferably represent optionally    methyl-substituted C₃-C₄-alkanediyl,-   G particularly preferably represents hydrogen (a) or represents one    of the groups

in which

M represents oxygen or sulphur,

-   R¹ particularly preferably represents C₁-C₈-alkyl, C₂-C₄-alkenyl,    methoxymethyl, ethoxymethyl, ethylthiomethyl, cyclopropyl,    cyclopentyl or cyclohexyl,

represents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-,methyl-, ethyl-, methoxy-, trifluoromethyl- ortrifluoromethoxy-substituted phenyl,

represents in each case optionally chlorine- or methyl-substitutedpyridyl or thienyl,

-   R² particularly preferably represents C₁-C₈-alkyl, C₂-C₄-alkenyl,    methoxyethyl, ethoxyethyl or represents phenyl or benzyl,-   R⁶ and R⁷ independently of one another particularly preferably    represent methyl, ethyl or together represent a C₅-alkylene radical    in which the C₃-methylene group is replaced by oxygen,-   W very particularly preferably represents hydrogen or methyl,-   X very particularly preferably represents chlorine, bromine or    methyl,-   Y and Z independently of one another each very particularly    preferably represent hydrogen, chlorine, bromine or methyl,-   A, B and the carbon atom to which they are attached very    particularly preferably represent saturated C₆-cycloalkyl in which    optionally one ring member is replaced by oxygen and which is    optionally monosubstituted by methyl, methoxy, ethoxy, propoxy or    butoxy,-   D very particularly preferably represents hydrogen,-   G very particularly preferably represents hydrogen (a) or represents    one of the groups

in which

-   M represents oxygen or sulphur,-   R¹ very particularly preferably represents C₁-C₈-alkyl,    C₂-C₄-alkenyl, methoxymethyl, ethoxymethyl, ethylmethylthio,    cyclopropyl, cyclopentyl, cyclohexyl or

represents optionally fluorine-, chlorine-, bromine-, methyl-, methoxy-,trifluoromethyl-, trifluoromethoxy-, cyano- or nitro-substituted phenyl,

represents in each case optionally chlorine- or methyl-substitutedpyridyl or thienyl,

-   R² very particularly preferably represents C₁-C₈-alkyl,    C₂-C₄-alkenyl, methoxyethyl, ethoxyethyl, phenyl or benzyl,-   R⁶ and R⁷ independently of one another each very particularly    preferably represent methyl, ethyl or together represent a    C₅-alkylene radical in which the C₃-methylene group is replaced by    oxygen.

Especial preference is given to active compound combinations comprisingcompounds of the formula (I)

(I)

Example No. W X Y Z R G m.p. ° C. I-1 H Br 5-CH₃ H OCH₃ CO-i-C₃H₇ 122I-2 H Br 5-CH₃ H OCH₃ CO₂—C₂H₅ 140-142 I-3 H CH₃ 5-CH₃ H OCH₃ H >220 I-4H CH₃ 5-CH₃ H OCH₃ CO₂—C₂H₅ 128 I-5 CH₃ CH₃ 3-Br H OCH₃ H >220 I-6 CH₃CH₃ 3-Cl H OCH₃ H 219 I-7 H Br 4-CH₃ 5-CH₃ OCH₃ CO-i-C₃H₇ 217 I-8 H CH₃4-Cl 5-CH₃ OCH₃ CO₂C₂H₅ 162 I-9 H CH₃ 4-CH₃ 5-CH₃ OCH₃

oil I-10 CH₃ CH₃ 3-CH₃ 4-CH₃ OCH₃ H >220 I-11 H CH₃ 5-CH₃ H OC₂H₅

oil I-12 CH₃ CH₃ 3-Br H OC₂H₅ CO-i-C₃H₇ 212-214 I-13 H CH₃ 4-CH₃ 5-CH₃OC₂H₅ CO-n-Pr 134 I-14 H CH₃ 4-CH₃ 5-CH₃ OC₂H₅ CO-i-Pr 108 I-15 H CH₃4-CH₃ 5-CH₃ OC₂H₅ CO-c-Pr 163and at least one active compound of compounds 1 to 29.

In addition, the active compound combinations may also comprise otherfungicidally, acaricidally or insecticidally active components which maybe admixed.

If the active compounds are present in the active compound combinationsaccording to the invention in certain weight ratios, the synergisticeffect is particularly pronounced. However, the weight ratios of theactive compounds in the active compound combinations may be variedwithin a relatively wide range. In general, the combinations accordingto the invention comprise active compounds of the formula (I) and theco-components in the preferred and particularly preferred mixing ratiosindicated in the table below:

-   -   the mixing ratios are based on weight ratios. The ratio is to be        understood as meaning active compound of the formula (I):        co-component

Particularly Preferred mixing preferred mixing Co-component ratio ratiobifenazate 5:1 to 1:20 1:1 to 1:10 abamectin 50:1 to 1:5 10:1 to 1:1acequinocyl 10:1 to 1:10 5:1 to 1:5 chlorfenapyr 10:1 to 1:10 5:1 to 1:5diafenthiuron 10:1 to 1:10 5:1 to 1:5 etoxazole 20:1 to 1:5 10:1 to 1:2azocyclotin 10:1 to 1:10 5:1 to 1:5 cyhexatin 10:1 to 1:10 5:1 to 1:5tebufenpyrad 20:1 to 1:10 10:1 to 1:5 fenpyroximate 10:1 to 1:10 5:1 to1:5 pyridaben 10:1 to 1:10 5:1 to 1:5 flufenoxuron 10:1 to 1:10 5:1 to1:5 bifenthrin 10:1 to 1:10 5:1 to 1:5 clofentezine 10:1 to 1:10 5:1 to1:5 fenbutatin oxide 10:1 to 1:10 5:1 to 1:5 tolylfluanid 5:1 to 1:501:1 to 1:5 pyrimidyl phenol 10:1 to 1:10 5:1 to 1:5 ethers (XVII-XIX)spinosad 10:1 to 1:10 5:1 to 1:5 ivermectin 50:1 to 1:5 10:1 to 1:1milbemectin 50:1 to 1:5 10:1 to 1:1 endosulfan 10:1 to 1:10 5:1 to 1:5fenazaquin 10:1 to 1:10 5:1 to 1:5 pyrimidifen 50:1 to 1:5 10:1 to 1:1triarathen 5:1 to 1:20 1:1 to 1:10 tetradifon 10:1 to 1:10 5:1 to 1:5propargit 10.1 to 1:10 5:1 to 1:5 hexythiazox 20:1 to 1:5 10:1 to 1:2bromopropylate 10:1 to 1:10 5:1 to 1:5 dicofol 10:1 to 1:10 5:1 to 1:5chinomethionat 10:1 to 1:10 5:1 to 1:5

The active compound combinations according to the invention are suitablefor controlling animal pests, preferably arthropods and nematodes, inparticular insects and arachnids found in agriculture, in animal health,in forests, in the protection of stored products and materials and inthe hygiene sector. They are active against normally sensitive andresistant species, and against all or individual developmental stages.The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.From the order of the Chilopoda, for example, Geophilus carpophagus,Scutigera spp.From the order of the Symphyla, for example, Scutigerella immaculata.From the order of the Thysanura, for example, Lepisma saccharina.From the order of the Collembola, for example, Onychiurus anmatus.From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp.,Schistocerca gregaria.From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica.From the order of the Denmaptera, for example, Forficula auricularia.From the order of the Isoptera, for example, Reticulitermes spp.From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp.,Damalinia spp.From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Triatoma spp.From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmaimophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp., Oulema oryzae.From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilaclmavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrusoryzophilus.From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis, Vespa spp.From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp., Liriomyza spp.From the order of the Siphonaptera, for example, Xenopsylla cheopis,Ceratophyllus spp.From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp., Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

The active compound combinations can be converted into the customaryformulations such as solutions, emulsions, wettable powders,suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound, and microencapsulations in polymericmaterials.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible, for example, to useorganic solvents as cosolvents. The following are essentially suitableas liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes and methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic materials such as highly-disperse silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, or else synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks; suitable emulsifiersand/or foam formers are: for example nonionic and anionic emulsifierssuch as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, or else protein hydrolysates; suitabledispersants are: for example lignin-sulphite waste liquors andmethylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchalizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with other activecompounds, such as insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth-regulating substances orherbicides. The insecticides include, for example, phosphates,carbamates, carboxylates, chlorinated hydrocarbons, phenylureas andsubstances produced by microorganisms.

Mixtures with other known active compounds such as herbicides or withfertilizers and growth regulators are also possible.

When used as insecticides, the active compound combinations according tothe invention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergists. Synergists are compounds which increase theaction of the active compounds, without it being necessary for thesynergist added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and stored-product pests, the activecompound combinations are distinguished by an excellent residual actionon wood and clay as well as good stability to alkali on limedsubstrates.

The active compound combinations according to the invention are not onlyactive against plant pests, hygiene pests and stored-product pests, butalso, in the veterinary medicine sector, against animal parasites(ectoparasites) such as hard ticks, soft ticks, mange mites, harvestmites, flies (stinging and licking), parasitizing fly larvae, lice, hairlice, bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp., Melophagus spp.From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattella germanica, Supella spp.From the subclass of the Acaria (Acarida) and the order of the Meta- andMesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp.,Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compound combinations according to the invention are alsosuitable for controlling arthropods which attack agricultural livestocksuch as, for example, cattle, sheep, goats, horses, pigs, donkeys,camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey-bees,other domestic animals such as, for example, dogs, cats, caged birds,aquarium fish and so-called experimental animals such as, for example,hamsters, guinea pigs, rats and mice. By controlling these arthropods,cases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey and the like) should be diminished, so that moreeconomical and simpler animal husbandry is possible by the use of theactive compound combinations according to the invention.

The active compound combinations according to the invention are used inthe veterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through method, suppositories, by parenteraladministration such as, for example, by injections (intramuscularly,subcutaneously, intravenously, intraperitoneally and the like),implants, by nasal administration, by dermal administration in the formof, for example, immersing or dipping, spraying, pouring-on,spotting-on, washing, dusting, and with the aid ofactive-compound-comprising moulded articles such as collars, ear tags,tail tags, limb bands, halters, marking devices and the like.

When used for cattle, poultry, domestic animals and the like, the activecompound combinations can be applied as formulations (for examplepowders, emulsions, flowables) comprising the active compounds in anamount of 1 to 80% by weight, either directly or after 100- to10,000-fold dilution, or they may be used as a chemical dip.

Moreover, it has been found that the active compound combinationsaccording to the invention show a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and withpreference, but not by way of limitation:

Beetles such asHylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis,Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis,Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus,Bostrychus capucins, Heterobostrychus brtmneus, Sinoxylon spec.,Dinodertis minutus.Dermapterans such asSirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.Termites such asKalotennes flavicollis, Cryptoteimes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.Bristle-tails such as Lepisma saccharina.

Industrial materials in the present context are understood as meaningnon-living materials such as, preferably, polymers, adhesives, glues,paper and board, leather, wood, timber products and paints.

The material which is to be protected from insect attack is veryespecially preferably wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention, or mixtures comprising it, are to beunderstood as meaning, for example:

Constriction timber, wooden beams, railway sleepers, bridge components,jetties, vehicles made of wood, boxes, pallets, containers, telephonepoles, wood lagging, windows and doors made of wood, plywood, chipboard,joinery, or timber products which quite generally are used in houseconstruction or building joinery.

The active compound combinations can be used as such, in the form ofconcentrates or generally customary formulations such as powders,granules, solutions, suspensions, emulsions or pastes.

The abovementioned formulations can be prepared in a manner known perse, for example by mixing the active compounds with at least one solventor diluent, emulsifier, dispersant and/or binder or fixative, waterrepellant, if desired desiccants and UV stabilizers, and if desiredcolorants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for protecting woodand timber products comprise the active compound according to theinvention in a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of composition or concentrate employed depends on the speciesand the abundance of the insects and on the medium. The optimal quantityto be employed can be determined in each case by test series uponapplication. In general, however, it will suffice to employ 0.0001 to20% by weight, preferably 0.001 to 10% by weight, of the activecompound, based on the material to be protected.

A suitable solvent and/or diluent is an organochemical solvent orsolvent mixture and/or an oily or oil-type organochemical solvent orsolvent mixture of low volatility and/or a polar organochemical solventor solvent mixture and/or water and, if appropriate, an emulsifierand/or wetter.

Organochemical solvents which are preferably employed are oily oroil-type solvents with an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C. Such oily and oil-typesolvents which are insoluble in water and of low volatility and whichare used are suitable mineral oils or their aromatic fractions ormineral-oil-containing solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

Mineral oils with a boiling range of 170 to 220° C., white spirit with aboiling range of 170 to 220° C., spindle oil with a boiling range of 250to 350° C., petroleum and aromatics with a boiling range of 160 to 280°C., oil of turpentine, and the like are advantageously used.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene are used.

The organic oily or oil-type solvents of low volatility and with anevaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C., and that the mixture is solubleor emulsifiable in this solvent mixture.

In a preferred embodiment, some of the organochemical solvent or solventmixture is replaced by an aliphatic polar organochemical solvent orsolvent mixture. Aliphatic organochemical solvents which containhydroxyl and/or ester and/or ether groups are preferably used, such as,for example, glycol ethers, esters or the like.

Organochemical binders used for the purposes of the present inventionare the synthetic resins and/or binding drying oils which are known perse and which can be diluted in water and/or dissolved or dispersed oremulsified in the organochemical solvents employed, in particularbinders composed of, or comprising, an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenol resin, hydrocarbon resin such as indene/coumarone resin,silicone resin, drying vegetable and/or drying oils and/or physicallydrying binders based on a natural and/or synthetic resin.

The synthetic resin employed as binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances mayalso be used as binders, in amounts of up to 10% by weight. In addition,colorants, pigments, water repellants, odour-masking agents, andinhibitors or anticorrosive agents and the like, all of which are knownper se, can be employed.

In accordance with the invention, the composition or the concentratepreferably comprises, as organochemical binders, at least one alkydresin or modified alkyd resin and/or a drying vegetable oil. Alkydresins which are preferably used in accordance with the invention arethose with an oil content of over 45% by weight, preferably 50 to 68% byweight.

Some or all of the abovementioned binder can be replaced by a fixative(mixture) or plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds, and also crystallizationor precipitation. They preferably replace 0.01 to 30% of the binder(based on 100% of binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate,phosphoric esters such as tributyl phosphate, adipic esters such asdi-(2-ethylhexyl)-adipate, stearates such as butyl stearate or amylstearate, oleates such as butyl oleate, glycerol ethers orhigher-molecular-weight glycol ethers, glycerol esters andp-toluenesulphonic esters.

Fixatives are based chemically on polyvinyl alkyl ethers such as, forexample, polyvinyl methyl ether, or ketones such as benzophenone andethylenebenzophenone.

Other suitable solvents or diluents are, in particular, water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective timber protection is achieved by industrial-scaleimpregnating processes, for example the vacuum, double-vacuum orpressure processes.

The active compound combinations according to the invention can at thesame time be employed for protecting objects which come into contactwith saltwater or brackish water, such as hulls, screens, nets,buildings, moorings and signalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the active compoundcombinations according to the invention have an outstanding antifoulingaction.

Using the active compound combinations according to the invention,allows the use of heavy metals such as, for example, in bis(trialkyltin)sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I)oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)tin,tributyltin oxide, molybdenum disulphide, antimony oxide, polymericbutyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltinfluoride, manganese ethylenebisthiocarbamate, zincdimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts andcopper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzincethylene-bisthiocarbamate, zinc oxide, copper(I)ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate andtributyltin halides to be dispensed with, or the concentration of thesecompounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

algicides such as2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,dichlorophen, diuron, endothal, fentin acetate, isoproturon,methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;fungicides such asbenzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,tolylfluanid and azoles such as azaconazole, cyproconazole,epoxyconazole, hexaconazole, metconazole, propiconazole andtebuconazole;molluscicides such asfentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb andtrimethacarb;or conventional antifouling active compounds such as4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium,copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridine-triphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide and2,4,6-trichlorophenylmaleiimide.

The antifouling compositions used comprise the active compoundcombinations according to the invention in a concentration of 0.001 to50% by weight, in particular 0.01 to 20% by weight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in saltwater.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compound combinations are also suitable for controllinganimal pests, in particular insects, arachnids and mites, which arefound in enclosed spaces such as, for example, dwellings, factory halls,offices, vehicle cabins and the like. They can be employed in domesticinsecticide products for controlling these pests. They are activeagainst sensitive and resistant species and against all developmentalstages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Deimatophagoides pteronissimus,Dennatophagoides forinae.From the order of the Araneae, for example, Aviculariidae, Araneidae.From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.From the order of the Isopoda, for example, Oniscus asellus, Porcellioscaber.From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.From the order of the Chilopoda, for example, Geophilus spp.From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.From the order of the Saltatoria, for example, Acheta domesticus.From the order of the Dermaptera, for example, Forficula auricularia.From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Farnia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans, Tipula paludosa.From the order of the Lepidoptera, for example, Acliroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Phthirus pubis.From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.They are used as aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and geneticengineering or by combinations of these methods, inclusive of thetransgenic plants and inclusive of the plant varieties protectable ornot protectable by plant breeders' rights. Plant parts are to beunderstood as meaning all above-ground and below-ground parts and organsof plants, such as shoot, leaf, flower and root, examples which may bementioned being leaves, needles, stalks, stems, flowers, fruit bodies,fruits, seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on the surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seed, also byapplying one or more coats.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention, better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to water or soilsalt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, better quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products are possiblewhich exceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferred and to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparts particularly advantageous usefulproperties (“traits”) to these plants. Examples of such properties arebetter plant growth, increased tolerance to high or low temperatures,increased tolerance to drought or to water or soil salt content,increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenseof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapevines), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are particularly emphasized are increased defense of the plantsagainst insects by toxins formed in the plants, in particular thoseformed by the genetic material from Bacillus thuringiensis (for exampleby the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2,Cry9c Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits that are furthermoreparticularly emphasized are the increased tolerance of the plants tocertain herbicidally active compounds, for example imidazolinones,sulphonylureas, glyphosate or phosphinotricin (for example the “PAT”gene). The genes which impart the desired traits in question can also bepresent in combination with one another in the transgenic plants.Examples of “Bt plants” which may be mentioned are maize cultivars,cotton cultivars, soya bean cultivars and potato cultivars which aresold under the trade names YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), StarLink® (for example maize),Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize cultivars,cotton cultivars and soya bean cultivars which are sold under the tradenames Roundup Ready® (tolerance to glyphosate, for example maize,cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, forexample oilseed rape), IMI® (tolerance to imidazolinones) and STS®(tolerance to sulphonylurea, for example maize). Herbicide-resistantplants (plants bred in a conventional manner for herbicide tolerance)which may be mentioned include the cultivars sold under the nameClearfield® (for example maize). Of course, these statements also applyto plant cultivars having these or still to be developed genetic traits,which plants will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the active compound mixturesaccording to the invention. The preferred ranges stated above for themixtures also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the mixturesspecifically mentioned in the present text.

The good insecticidal and acaricidal action of the active compoundcombinations according to the invention can be seen from the exampleswhich follow. While the individual active compounds show weaknesses intheir action, the combinations show an action which exceeds a simple sumof actions.

A synergistic effect in insecticides and acaricides is always presentwhen the action of the active compound combinations exceeds the total ofthe actions of the active compounds when applied individually.

The expected action for a given combination of two active compounds canbe calculated as follows, using the formula of S. R. Colby, Weeds 15(1967), 20-22:

If

-   X is the kill rate, expressed as % of the untreated control, when    employing active compound A at an application rate of m g/ha or in a    concentration of m ppm,-   Y is the kill rate, expressed as % of the untreated control, when    employing active compound B at an application rate of m g/ha or in a    concentration of n ppm and-   E is the kill rate, expressed as % of the untreated control, when    employing active compounds A and B at application rates of m and n    g/ha or in a concentration of m and n ppm,    then

$E = {X + y - \frac{X \cdot Y}{100}}$

If the actual insecticidal kill rate exceeds the calculated value, theaction of the combination is superadditive, i.e. a synergistic effect ispresent. In this case, the actually observed kill rate must exceed thevalue calculated using the above formula for the expected kill rate (E).

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals have been killed.

EXAMPLE A Critical Concentration Test/Soil Insects Treatment ofTransgenic Plants

Test insect: Diabrotica balteata—larvae in soilSolvent: 7 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil. Here, theconcentration of the active compound in the preparation is virtuallyirrelevant, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.25 l pots and these are allowed to stand at 20° C.

Immediately after preparation, 5 pre-germinated maize corns of thevariety YIELD GUARD (trade mark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the test insects in question are placed into thetreated soil. After a further 7 days, the efficacy of the activecompound is determined by counting the maize plants that have emerged (1plant=20% efficacy).

EXAMPLE B Heliothis virescens Test Treatment of Transgenic Plants

Solvent: 7 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (glycine max) of the variety Roundup Ready (trade markof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and are populated withthe tobacco budworm Heliothis virescens while the leaves are stillmoist.

After the desired period of time, the kill of the insects is determined.

1-8. (canceled)
 9. A composition comprising a mixture of synergisticallyeffective amounts of (1) a compound of the formula (Ia)

in which W is H, X is CH₃, Y is 5-CH₃, Z is H, R is OCH₃, and G isCO₂—C₂H₅, and (2) at least one compound selected from the groupconsisting of (i) bifenazate at a ratio of the compound of formula (Ia)to bifenazate of from 1:1 to 1:10, (ii) abamectin at a ratio of thecompound of formula (Ia) to abamectin of from 10:1 to 1:1, and (iii)spinosad at a ratio of the compound of formula (Ia) to spinosad of from5:1 to 1:5.
 10. A method for controlling insects and/or acaridscomprising allowing an effective amount of a composition according toclaim 9 to act on said insects and/or acarids and/or their habitat. 11.A process for preparing an insecticidal and acaricidal compositioncomprising mixing a composition according to claim 9 with extendersand/or surfactants.